Reactive, low molecular weight, viscous poly(1-olefins) and copoly(1-olefins) and their method of manufacture

ABSTRACT

Catalysts and processes are described to make low molecular weight, essentially terminally-unsaturated, viscous poly(1-olefin) or copoly(1-olefin) having a high terminal vinylidine content from a feed stock containing one or more 1-olefin and other volatile hydrocarbon liquids using a Ziegler catalyst made from a Group IVb metallocene and an aluminoxane cocatalyst, particularly bis(cyclopentadienyl) and bis(indenyl) titanium(IV), zirconium(IV) or hafnium(IV) compounds and methylaluminoxane. A particularly useful feed stock is a refinery stream containing 1-olefins and isobutylene which is used to make polyisobutylene. The reactive, essentially terminally-unsaturated, viscous poly(1-olefin) or copoly(1-olefin) can be functionalized to make a number of products useful as sealants, petroleum additives, adhesives, and the like by reacting the terminal vinylidine linkage with an aromatic, an epoxidation agent, a silylation agent, maleic anhydride, carbon monoxide and hydrogen, hydrogen, a halogen, a hydrohalogen, and the like.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a continuation of application Ser. No. 08/576,573filed Dec. 21, 1995, now abandoned, which is a continuation ofapplication Ser. No. 08/211,925 filed Apr. 28, 1994, now abandoned,which is a 371 of PCT/US93/04991 filed May 26, 1993, which is acontinuation-in-part of application Ser. No. 07/889,045 filed May 26,1992, now abandoned.

BACKGROUND OF THE INVENTION

This invention relates to the catalyzed preparation and reactions of areactive, low molecular weight, viscous, essentially-1-olefin-containingpoly(1-olefin) or copoly(1-olefin) prepared employing a catalystcomprising a Periodic Group IVb metallocene and an aluminoxane, and moreparticularly to the catalyzed preparation and reactions of a reactive,low molecular weight, viscous essentially-1-olefin-containingpoly(1-olefin) or copoly(1-olefin) prepared from a feed stock containingone or more C₃ to C₂₀ 1-olefin and other volatile hydrocarbon liquids.The viscous polymers of this invention are essentiallyterminally-unsaturated poly(1-olefin)s or copoly(1-olefin)s with suchterminal unsaturation being more than 80% vinylidene type made by acatalyst system using a Periodic Group IVb metallocene and analuminoxane.

A number of patents and other publications have described the use oftransition element, including those of Periodic Group IVb,metallocene/aluminoxane catalysts (supported or unsupported) for thepolymerization of 1-olefins and certain cycloalkenes such as ethylene,propylene, butene1, hexene-1, octene-1, styrene, cyclobutene,cyclopentene, and norbornene. The catalysts are said to have advantageswhich include increased polymerization activity, the ability to producesome terminal unsaturation and a narrow molecular weight distribution inthe product polymer, and the ability to precisely choose polymer stereoregularity. See U.S. Pat. Nos. 4,530,914; 4,752,597; 4,808,561; and5,001,244. See also U.S. Pat. No. 4,542,199 where polymerization ofolefins of formula CH₂ CHR in which R is H or C₁ to C₁₀ alkyl isdescribed, the Periodic Group IVb metallocene employed is abis(cyclopentadienyl) transition element particularly zirconium, andcopolymerization with alpha-omega dienes is taught. In Example 4 of thatpatent, bis(cyclopentadienyl)zirconium dichloride and aluminoxane areused to give atactic polypropylene of molecular weight 5000.

Typically, a high ratio of methylaluminoxane(MAO) cocatalyst tometallocene must be used (approximately 300/1 or more). But see U.S.Pat. No. 4,808,561 wherein the reaction product of a mixture ofmetallocene and aluminoxane in the presence of a support is said toproduce a catalyst which will polymerize olefins at an acceptable ratewithout the presence of an objectional excess of aluminum.

Also, see U.S. Pat. No. 4,752,597 which describes the use of a solidreaction product of a transition metal metallocene, particularly a GroupIVb metallocene, with aluminoxane cocatalyst to effectively polymerizeolefin wherein the molar ratio of metallocene to aluminoxane liesbetween 1:12 and 1:100. It has also been reported in U.S. Pat. No.5,001,244 that the addition of a boron compound such astris(perfluorophenyl)boron is able to reduce or eliminate the need forsuch a high aluminum to metallocene ratio.

In U.S. Pat. No. 5,162,466, use of a cyclo(pentadienyl)dicarbollidecomplexes of titanium, zirconium and hafnium as catalyst in the absenceof a cocatalyst, such as an aluminoxane, is taught for polymerization ofethylene or copolymerization of ethylene with a C₃ to C₈ alpha olefin.

Stanford Research Institute reports that the use of one of thesemetallocene Ziegler catalysts to make polyethylene is beingcommercialized and the process is described as capable of preparinglinear low density polyethylenes of superior physical properties.

It is reported by W. Kaminsky et al. in Bull. Soc. Chim. Belg. 99(2),103-111(1990) that simple zirconium metallocenes polymerizepropylene to atactic polymer. The reference also shows that chiral,ethylene-bridged bis(tetrahydroindenyl)zirconium dichloride andmethylaluminoxane catalyst can produce isotactic polypropylene.

See also Polymerization of Propene and Butene with a Chiral Zirconoceneand Methylalumoxane as Cocatalyst by W. Kaminsky et al. in Angew. Chem.Int. Ed. Engl. 2 4 No. 6, pp 507-508 (1985). Reisconi et al. in J. Am.Chem. Soc. 114 1025-1032(1992) states that polymerization of propylenewith a bis(indenyl)zirconium dichloride (Ind₂ ZrCl₂) and MAO catalystleads to termination by beta hydrogen elimination and thus apolypropylene product which has some terminal unsaturation of thevinylidene type. In WO 9111488 to Exxon, a copolymeric wax crystalmodifier of number average molecular weight between 300 and 15,000 madefrom ethylene and at least one alpha-olefin and containing at least 40mol % ethylene is made using a metallocene catalyst. The copolymer hasat least 30% of the polymer chains exhibiting terminal ethenylidineunsaturation.

In U.S. Pat. No. 4,658,078 use of (a) cyclo(pentadienyl)zirconium orhafnium metallocene and (b) an aluminoxane catalyst, with atom ratio ofAl to Zr or Hf of 1 to 100, is taught for dimerizing a C₃ to C₃₂ alphaolefin at temperatures between -60° C. and 280° C.

In U.S. Pat. No. 4,704,491 copolymerizing ethylene and a C₃ to C₂₀alpha-olefin in the presence of a compound of Periodic Group IVb and analuminoxane catalyst is taught for making a random copolymer.

In U.S. Pat. No. 5,017,665, use of a supported, bridgedbis(indenyl)zirconium dichloride/aluminoxane catalyst is taught for thecopolymerization of a mixture of ethylene and 1,4-diene.

In U.S. Pat. No. 5,077,255, copolymerizing ethylene and a C₃ to C₂₀alpha-olefin in the presence of a compound of Periodic Group IVb and analuminoxane catalyst is taught for making a random copolymer having anumber average molecular weight above 20,000 and an average of at least30% of the polymer chains contain terminal ethylidene unsaturation.

In U.S. Pat. No. 5,151,204, use of a supported reaction product of (a)at least one metallocene of a metal of Group IVb, Vb, and VIb, (b) anon-metallocene transition metal containing compound of a Group IVb, Vb,and VIb metal and (c) an aluminoxane catalyst is taught for thecopolymerization of a mixture of ethylene and other mono and diolefins.

In Japanese Patent No. 01,132,605 it is reported that a poly(1-olefin)made with bis(cyclopentadienyl)zirconium dichloride andmethylaluminoxane can be reacted with perbenzoic acid to form epoxide.

In European Patent Application No. 0 268 214, it is reported thatpropylene oligomers were made with an alkyl substituted cyclopentadienylcompound of zirconium and/or hafnium and a condensation product oforganoaluminum compound and water. In Comparative Examples 1, 2, and 3,however, using three non-substituted cyclopentadienyl compounds, i.e.,bis(cyclopentadienyl)zirconium, hafnium, and titanium dichloride, apolymerization of propylene reaction took place preferentially topropylene oliogomerization reaction and products were all high polymerswhich predominantly had vinylidene group as terminal unsaturated group.

Terminal unsaturation of the vinylidene type can be very important topolymer reactivity in the case of low molecular weight, viscouspolybutenes when being functionalized and a number of ways to enhance ithave been suggested. For example, use of a BF₃ catalyst cansubstantially reduce the amount of tri- and tetra-substituted terminalolefin in the polymerization and produce more vinylidene type oftermination. Terminal unsaturation of the proper type could also be veryhelpful to the reactivity of poly(1-olefins).

Now it has been found that a low molecular weight, viscousessentially-1-olefin-containing poly(1-olefin) or copoly(1-olefin) canbe formed from a feed stock containing one or more C₃ to C₂₀ 1-olefinand other volatile hydrocarbons by selectively polymerizing the1-olefins with a Ziegler type metallocene and aluminoxane catalyst.Furthermore, viscous poly(1-olefins) and copoly(1-olefins) so formed arealmost completely terminally unsaturated and their terminal unsaturationis, advantageously, largely of the vinylidene type. Such viscouspolymers are very reactive because of the presence of the high degree ofunsaturation and the extensive vinylidene termination and therefore canbe easily functionalized in high yields by conventional methods to makea range of useful products. Products and process are described here inwhich the terminal olefinic linkage, for example, has been used toalkylate an aromatic ring, or has undergone an Ene reaction, anaddition, a hydroformylation, a hydrosilylation, a chlorination, and thelike. The lack of polymerization activity of these catalysts towardsolefins other than 1-olefins allows a common refinery streams containinga mixture of olefins including isobutylene to be effectively polymerizedto make polyisobutene by the usual acid catalyzed process as well asproduce the low molecular weight, viscous poly(1-olefin) orcopoly(1-olefin) of this invention. This multistep procedure involves adifferent catalyst for each polymerization and utilizes more fully thecomponents of the refinery stream which after polyisobutylene formationis customarily used for fuel.

SUMMARY OF THE INVENTION

The invention contained herein is a process to form an essentiallyterminally-unsaturated, viscous, essentially-1-olefin-containingpoly(1-olefin) or copoly(1-olefin) of molecular weight between about 300and about 10,000 that exhibits a terminal vinylidene content of morethan 80% which comprises polymerizing a feed comprising one or more C₃to C₂₀ 1-olefin using a catalyst comprising a Periodic Group IVbmetallocene and aluminoxane cocatalyst, said mixture containing at leastabout 1 wt. % isobutylene.

In another aspect, the invention is a process to form an essentiallyterminally-unsaturated, viscous, essentially-1-olefin-containingpoly(1-olefin) or copoly(1-olefin) which process comprises polymerizingunder fluid phase conditions, preferably liquid phase conditions, a feedstock comprising more than 1 weight percent of at least one volatilehydrocarbon liquid and less than 99 weight percent based on total feedstock of one or more C₃ to C₂₀ 1-olefin using a catalyst systemcomprising a titanium(IV), zirconium(IV) or hafnium(IV) metallocene andan aluminoxane cocatalyst to form a poly(1-olefin) or copoly(1-olefin)having molecular weight in a range from about 300 to about 10,000 andterminal vinylidene content of more than 80%. In practice of thisinvention catalyst systems using a bis(cyclopentadienyl) or bis(indenyl)titanium(IV), zirconium(IV) and hafnium(IV) compound are particularlyuseful, preferably, bis(cyclopentadienyl)zirconium dichloride andbis(indenyl)-zirconium dichloride. Advantageously, the cocatalyst is alinear methylaluminoxane and/or cyclic methylaluminoxane.

In one embodiment of the process of this invention the feed stockcontains at least about 0.1 wt. % of isobutylene, the catalyst systemcomprises bis(indenyl)zirconium dichloride and methylaluminoxanecocatalyst, and wherein a poly(1-olefin) or copoly(1-olefin) havingmolecular weight is a range from about 300 to about 5000, terminalvinylidene content is greater than 90% is formed.

In a further embodiment of the process of this invention the feed stockadditionally contains up to about 70% by weight of an alpha-omega diene.

In another aspect, the invention is an essentiallyterminally-unsaturated, viscous, essentially-1-olefin containingpoly(1-olefin) or copoly(1-olefin) polymer having molecular weight in arange from about 300 to about 10,000 and terminal vinylidene content ofmore than 80%, which poly(1-olefin) or copoly(1-olefin) is made from afeed stock comprising more than 1 weight percent of at least onevolatile hydrocarbon liquid and less than 99 weight percent based ontotal feed stock of one or more C₃ to C₂₀ 1-olefin using a catalystsystem comprising a titanium(IV), zirconium(IV) or hafnium(IV)metallocene and an aluminoxane cocatalyst.

In preferred embodiments the polymers of this invention are formed by acatalyst system using bis(cyclopentadienyl)zirconium dichloride and/orbis(indenyl)zirconium dichloride and a linear methylaluminoxane and/orcyclic methylaluminoxane cocatalyst.

In a further aspect, the invention is process to sequentially frompolyisobutylene and an essentially terminally-unsaturated, viscous,essentially-1-olefin-containing poly(1-olefin) or copoly(1-olefin) ofmolecular weight between about 300 and about 10,000 that exhibits aterminal vinylidene content of more than 80% from a feed stockcomprising more than 1 weight percent of at least one volatilehydrocarbon liquid and less than 99 weight percent based on total feedstock of one or more C₃ to C₂₀ 1-olefin, the feed containing betweenabout 0.1 and 55 wt. % isobutylene which process comprises the steps:

(a) polymerizing the 1-olefin using a catalyst system comprising atitanium(IV), zirconium(IV) or hafnium(IV) metallocene and aluminoxanecocatalyst to form poly(1-olefin) or copoly(1-olefin); and

(b) polymerizing the isobutylene with an acid catalyst to formpolyisobutylene.

In another aspect, the invention is a product formed by reaction ofphenol or substituted phenol with essentially terminally-unsaturated,viscous, essentially-1-olefin-containing poly(1-olefin) orcopoly(1-olefin) having molecular weight in a range from about 300 toabout 10,000 and terminal vinylidene content of more than 80% whichpoly(1-olefin) or copoly(1-olefin) is made from a feed stock comprisingmore than 1 weight percent of at least one volatile hydrocarbon liquidand less than 99 weight percent based on total feed stock of one or moreC₃ to C₂₀ 1-olefin using a catalyst system comprising a titanium(IV),zirconium(IV) or hafnium(IV) metallocene and an aluminoxane cocatalystto form a largely para-alkylated product of reaction. Preferred productsof this reaction are formed using a catalyst system ofbis(cyclopentadienyl)zirconium dichloride and/or bis(indenyl)zirconiumdichloride, and a linear methylaluminoxane and/or cyclicmethylalumninoxane cocatalyst. Preferred products of this reaction arealso formed using feed stock containing isobutylene in an amount of fromabout 0.1 weight percent to about 55 weight percent isobutylene based ontotal weight of feed stock.

In another aspect, the invention is a product formed by reaction ofhydrogen peroxide or a peracid with essentially terminally-unsaturated,viscous, essentially-1-olefin-containing poly(1-olefin) orcopoly(1-olefin) having molecular weight in a range from about 300 toabout 10,000 and terminal vinylidene content of more than 80% whichpoly(1-olefin) or copoly(1-olefin) is made from a feed stock comprisingmore than 1 weight percent of at least one volatile hydrocarbon liquidand less than 99 weight percent based on total feed stock of one or moreC₃ to C₂₀ 1-olefin using a catalyst system comprisingbis(indenyl)zirconium(IV) dichloride and an aluminoxane cocatalyst toform the corresponding epoxide product of reaction. Preferred productsof this reaction are formed using a catalyst system ofbis(cyclopentadienyl)zirconium dichloride and/or bis(indenyl)zirconiumdichloride, and a linear methylaluminoxane and/or cyclicmethylaluminoxane cocatalyst. Preferred products of this reaction arealso formed using feed stock containing isobutylene in an amount of fromabout 0.1 weight percent to about 55 weight percent isobutylene based ontotal weight of feed stock.

In yet another aspect, the invention is a product formed by reaction ofa silylating agent containing at least one silicon-hydrogen bond withessentially terminally-unsaturated, viscous,essentially-1-olefin-containing poly(1-olefin) or copoly(1-olefin)having molecular weight in a range from about 300 to about 10,000 andterminal vinylidene content of more than 80% which poly(1-olefin) orcopoly(1-olefin) is made from a feed stock comprising more than 1 weightpercent of at least one volatile hydrocarbon liquid and less than 99weight percent based on total feed stock of one or more C₃ to C₂₀1-olefin using a catalyst system comprising a titanium(IV),zirconium(IV) or hafnium(IV) metallocene and an aluminoxane cocatalystto form the corresponding terminally silylated poly(1-olefin) orcopoly(1-olefin) product of reaction. Preferred products of thisreaction are formed using a catalyst system ofbis(cyclopentadienyl)zirconium dichloride and/or bis(indenyl)zirconiumdichloride, and a linear methylaluminoxane and/or cyclicmethylaluminoxane cocatalyst. Preferred products of this reaction arealso formed using feed stock containing isobutylene in an amount of fromabout 0.1 weight percent to about 55 weight percent isobutylene based ontotal weight of feed stock.

In a further aspect, the invention is a product formed by reaction ofmaleic anhyride with essentially terminally-unsaturated, viscous,essentially-1-olefin-containing poly(1-olefin) or copoly(1-olefin)having molecular weight in a range from about 300 to about 10,000 andterminal vinylidene content of more than 80% which poly(1-olefin) orcopoly(1-olefin) is made from a feed stock comprising more than 1 weightpercent of at least one volatile hydrocarbon liquid and less than 99weight percent based on total feed stock of one or more C₃ to C₂₀1-olefin using a catalyst system comprising a titanium(IV),zirconium(IV) or hafnium(IV) metallocene and an aluminoxane cocatalystto form the corresponding succinic anhydride product of reaction.Preferred products of this reaction are formed using a catalyst systemof bis(cyclopentadienyl)zirconium dichloride and/orbis(indenyl)zirconium dichloride, and a linear methylaluminoxane and/orcyclic methylaluminoxane cocatalyst. Preferred products of this reactionare also formed using feed stock containing isobutylene in an amount offrom about 0.1 weight percent to about 55 weight percent isobutylenebased on total weight of feed stock.

In still a further aspect, the invention is a product formed by reactionof carbon monoxide and hydrogen with essentially terminally-unsaturated,viscous, essentially-1-olefin-containing poly(1-olefin) orcopoly(1-olefin) having molecular weight in a range from about 300 toabout 10,000 and terminal vinylidene content of more than 80% whichpoly(1-olefin) or copoly(1-olefin) is made from a feed stock comprisingmore than 1 weight percent of at least one volatile hydrocarbon liquidand less than 99 weight percent based on total feed stock of one or moreC₃ to C₂₀ 1-olefin using a catalyst system comprising a titanium(IV),zirconium(V) or hafnium(IV) metallocene and an aluminoxane cocatalyst toform the corresponding alcohol product of reaction. Preferred productsof this reaction are formed using a catalyst system ofbis(cyclopentadienyl)zirconium dichloride and/or bis(indenyl)zirconiumdichloride, and a linear methylaluminoxane and/or cyclicmethylaluminoxane cocatalyst. Preferred products of this reaction arealso formed using feed stock containing isobutylene in an amount of fromabout 0.1 weight percent to about 55 weight percent isobutylene based ontotal weight of feed stock.

In a further aspect, the invention is a product formed by reaction ofhydrogen with essentially terminally-unsaturated, viscous,essentially-1-olefin-containing poly(1-olefin) or copoly(1-olefin)having molecular weight in a range from about 300 to about 10,000 andterminal vinylidene content of more than 80% which poly(1-olefin) orcopoly(1-olefin) is made from a feed stock comprising more than 1 weightpercent of at least one volatile hydrocarbon liquid and less than 99weight percent based on total feed stock of one or more C₃ to C₂₀1-olefin using a catalyst system comprising a titanium(IV),zirconium(IV) or hafnium(IV) metallocene and an aluminoxane cocatalystto form a largely saturated product of reaction. Preferred products ofthis reaction are formed using a catalyst system ofbis(cyclopentadienyl)zirconium dichloride and/or bis(indenyl)zirconiumdichloride, and a linear methylaluminoxane and/or cyclicmethylaluminoxane cocatalyst. Preferred products of this reaction arealso formed using feed stock containing isobutylene in an amount of fromabout 0.1 weight percent to about 55 weight percent isobutylene based ontotal weight of feed stock.

In another aspect, the invention is a product formed by reaction ofaliphatic diamine with chlorinated polymer formed by reaction ofchlorine with essentially terminally-unsaturated, viscous,essentially-1-olefin-containing poly(1-olefin) or copoly(1-olefin)having molecular weight in a range from about 300 to about 10,000 andterminal vinylidene content of more than 80% which poly(1-olefin) orcopoly(1-olefin) is made from a feed stock comprising more than 1 weightpercent of at least one volatile hydrocarbon liquid and less than 99weight percent based on total feed stock of one or more C₃ to C₂₀1-olefin using a catalyst system comprising a titanium(IV),zirconium(IV) or hafnium(IV) metallocene and an aluminoxane cocatalystto form an aminated product of reaction. Preferred products of thisreaction are formed using a catalyst system ofbis(cyclopentadienyl)zirconium dichloride and/or bis(indenyl)zirconiumdichloride, and a linear methylaluminoxane and/or cyclicmethylaluminoxane cocatalyst. Preferred products of this reaction arealso formed using feed stock containing isobutylene in an amount of fromabout 0.1 weight percent to about 55 weight percent isobutylene based ontotal weight of feed stock.

In a further aspect, the invention is an essentiallyterminally-unsaturated, viscous, essentially-1-olefin-containingpoly(1-olefin) or copoly(1-olefin) of molecular weight between about 300and about 10,000 that exhibits a terminal vinylidene content of morethan 80% which is made from a feed comprising one or more C₃ to C₂₀1-olefin using a catalyst comprising a Periodic Group IVb metalloceneand an aluminoxane cocatalyst, said feed containing at least about 1 wt.% isobutylene. In still a further aspect, the invention is a process toform an essentially terminally-unsaturated, viscous,essentially-1-olefin-containing poly(1-olefin) or copoly(1-olefin) ofmolecular weight between about 300 and about 10,000 that exhibits aterminal vinylidene content of more than 80% comprising polymerizing afeed containing one or more olefin selected from the group consisting ofC₃ to C₂₀ 1-olefins with a catalyst comprising abis(indenyl)titanium(IV), zirconium(IV) or hafnium(IV) compound and analuminoxane cocatalyst. In yet another aspect, the invention is thereaction of a phenol or substituted phenol, an epoxidation agent, asilylating agent having at least one silicon-hydrogen bond, maleicanhydride, or carbon monoxide and hydrogen (hydroformylation) with anessentially terminally-unsaturated, viscous,essentially-1-olefin-containing poly(1-olefin) or copoly(1-olefin) ofmolecular weight between about 300 and about 10,000 that exhibits aterminal vinylidene content of more than 80% which is made from a feedcomprising one or more C₃ to C₂₀ 1-olefin using a catalyst comprising atitanium(IV), zirconium(IV) or hafnium(IV) metallocene and analuminoxane cocatalyst to form the corresponding largely para-alkylatedphenol or substituted phenol, epoxide, a terminally silylatedpoly(1-olefin) or copoly(1-olefin), succinic anhydride, alcohol, orsaturated hydrocarbon. And in still another aspect, the invention is aprocess to sequentially form polyisobutylene and an essentiallyterminally-unsaturated, viscous, essentially-1-olefin-containingpoly(1-olefin) or copoly(1-olefin) of molecular weight between about 300and about 10,000 that exhibits a terminal vinylidene content of morethan 80% from a feed comprising one or more C₃ to C₂₀ 1-olefins, saidfeed contains between about 0.1 and 55 wt. % isobutylene whichcomprises:

polymerizing said feed using a catalyst comprising a titanium(IV),zirconium(IV) or hafnium(IV) metallocene and an aluminoxane cocatalystto form said poly(1-olefin) or copoly(1-olefin); and

polymerizing said isobutylene with an acid catalyst to form saidpolyisobutylene.

DETAILED DESCRIPTION OF THE INVENTION

The Ziegler catalysts which are suitable for this invention are composedimportantly of two components. One component is a Periodic Group IVbmetallocene, preferably a titanium(IV), zirconium(IV) or hafnium(IV)metallocene and the other is an aluminoxane. The organic moiety of themetallocene is preferably cyclopentadienyl, indenyl or a lower alkylderivative thereof such as a lower-alkyl-substituted cyclopentadienyl orindenyl. Examples are bis(pentamethylcyclopentadienyl) or anethylene-bridged bis indenyl compound (at least with monomers that itdoes not give isotactic polymers with). The zirconium(IV) metallocenesare more preferred, as they give molecular weights in the 1000 to 2000number average range in the convenient 30 to 80° C. range, andbis(indenyl)zirconium dichloride is the most preferred metallocene.

The aluminoxanes are made generally by careful hydrolysis of atrialkylaluminum, more preferably trimethylaluminum which makesmethylaluminoxane, and may be the linear or cyclic variety ofaluminoxane or a mixture of both. This type of Ziegler catalyst unlikethe widely used titanium trichloride/aluminum alkyl catalyst forpropylene polymerization is generally soluble in aromatic solvents suchas benzene, toluene and the like as may be understood by one skilled inthe art. The molar amount of aluminoxane used in the catalyst isgenerally considerably greater than that of the metallocene used.Generally, molar ratios of about 20 to about 300 (aluminoxane tometallocene) or more are used, although methods have been devised toreduce the amount of aluminoxane as maybe understood by one skilled inthe art. For example, the catalyst may contain a boron compound such astris(perfluorophenyl)boron which can be effective in reducing oreliminating the amount of aluminoxane needed.

Generally, the metallocene and aluminoxane are individually combinedwith the olefin to be polymerized, and the order of combination does notappear critically important. It is not necessary to combine themetallocene and aluminoxane first and isolate a solid which is then usedas the catalyst by addition to the polymerization mix.

Feed stocks which are suitable for this invention are composedimportantly of two components. One component is a one or more C₃ to C₂₀1-olefin, preferably C₃ to C₁₀ 1-olefin, more preferably one or more1-olefin selected from the group consisting of propene, 1-butene,1-pentene, and 1-hexene, and most preferably 1-butene, 1-pentene, and/or1-hexene. The other essential component of such feed stocks is anotherhydrocarbon (non-1-olefin), preferably one or more volatile hydrocarbonliquid. Furthermore, feed stocks which are suitable for this inventionare substantially free of nitrogen, sulfur, and oxygen containingcompounds and like compounds which can deactivate the catalyst systemsof this invention.

Advantageously, the volatile hydrocarbon liquid components of the feedstock are in the liquid phase at conditions of polymerization, but havesufficient volatility, relatively low normal boiling temperatures, suchthat these volatile hydrocarbon liquid can be separated from theessentially terminally-unsaturated, viscous,essentially-1-olefin-containing poly(1-olefin) or copoly(1-olefin)products having number average molecular weight in a range from about300 to about 10,000, by a reduction of pressure at temperatures belowabout 250° C.

The olefin feed to make the low molecular weight, viscous polymers ofthis invention contains one or more C₃ to C₂₀ 1-olefin. A particularlypreferred feed is a refinery stream sometimes referred to as abutane-butylene stream (BB stream) which contains substantial amounts ofC₄ hydrocarbons such as isobutylene, 1-butene, 2-butene and butanetogether with propene, propane and small amounts of higher hydrocarbons.Such streams are used in the manufacture of poly(isobutylene). Otherpreferred feeds are a BB stream after the isobutylene content has beenlargely or completely polymerized by an acid catalyst such as aluminumchloride or boron trifluoride which is generally rich in propylene and1-butene (lean BB), and raffinates I and II which are feeds derived fromabeam cracking units typically containing between about 55 and 0.1 wt. %isobutylene. Propene and 1-butene and their mixtures are also preferredfeeds to the process of this invention.

When the olefin feed contains isobutylene, it is present in an amountbetween about 0.1 wt. % and about 55 wt. %, more preferably betweenabout 1 wt. % and 55 wt. %, and most preferably between about 5 wt. %and 55 wt. %.

Feed stocks which are suitable for this invention include abutane-butene feed stock having an approximate composition of 8%propane, 9% propene, 39% isobutane, 14% 1-butene, 12% n-butane, 2%isobutylene 15% cis and trans 2-butenes, 0.5% butadiene and smallamounts (less than 1%) of other hydrocarbons). Other butane-butene feedstocks suitable for this invention include feed stocks having anapproximate composition 4% isobutane, 28% 1-butene, 10% n-butane, 42%isobutylene, 16% cis and trans 2-butenes, and small amounts (less than1%) of other hydrocarbons) and a butane-butene feed stock having anapproximate composition 8% isobutane, 46% 1-butene, 17% n-butane, 27%cis and trans 2-butenes, and small amount (less than 1%) of otherhydrocarbons). Other feed stocks which are suitable for this inventioninclude pentane-pentene feed stocks varying in the relative amount of1-pentene from 5% 1-pentene and 95% pentane to 50% 1-pentene and 50%pentane.

Copolymers made from one or more 1-olefin and a diene may be made.Preferably a diene with one double bond substituted by a R group (tosuppress any cross linking by the added olefinic linkage) such asisoprene, 7-methyl-1,6-octadiene, 4-vinylcyclohexene, and the like maybe used in the inventive process. The addition of up to about 70 wt. %,more preferably up to about 50 wt. % to the polymerization feed of suchdiene, more preferably an alpha-omega diene, allows non-terminalunsaturation to be included in the inventive polymers which can providefor cross linking and alteration of the polymer properties.

The terminally unsaturated, viscous polymer of this invention isessentially a poly(1-olefin) or copoly(1-olefin). By essentially ismeant more than about a 95% and, more preferably, more than about a 98%1-olefin content in the polymer chains except where, for example, analpha-omega diene is added as described above. The catalyst of theinvention appears to not substantially cause the polymerization ofolefinic monomers other than 1-olefins. The product polymers alsopreferably have a number average molecular weight (M_(n)) between about300 and about 10,000, more preferably between about 300 and about 5000,and most preferably about 400 and about 3000 when measured by gelpermeation chromatography. The polymer chains of the viscous polymers ofthis invention are essentially terminally-unsaturated. By essentiallyterminally-unsaturated is meant preferably more than about 90% of thepolymer chains contain unsaturation, more preferably more than about95%, and most preferably more than about 99% of the polymer chains inthe product polymer contain terminal unsaturation. The terminalunsaturation is preferably more than about 80%, more preferably morethan about 90%, and, most preferably, more than about 95% of thevinylidene type.

The high degree of vinylidene type unsaturation makes the viscouspolymers of this invention very reactive in the typicalfunctionalization reactions which olefinic linkages undergo such asaddition, hydroformylation, hydrosilylation, Ene reactions such as aDiels Alder, alkylation, and the like.

The temperature of polymerization is determined in part by the molecularweight of the polymer to be made. As may be understood by one skilled inthe art, the molecular weight is in part determined by the temperature.However, the composition of the catalyst is also able to influence themolecular weight. Higher temperatures generally lead to lower molecularweights. A temperature in the range of about -80° C. to about 150° C.may be used depending upon the use to which the polymer product is to beput. More preferably, the polymerization temperature is about ambient to100° C., most preferably between about 50 and 100° C. for convenience ofthe polymerization operation.

The inventive catalysts made from metallocene and aluminoxane cocatalystcan be used unsupported or supported by compositing them with a typicalinorganic oxide support material used for this type of Ziegler catalystas can be understood by one skilled in the art. The polymerizationprocess utilizing the catalysts may be a suspension, solution or gasphase polymerization.

By viscous is meant polymers which undergo cold flow at molecularweights in the above set forth ranges at ambient temperature.

One of the more useful functionalization reactions on the polymers ofthis invention is the use of the viscous, terminally unsaturatedpoly(1-olefins) to alkylate an aromatic compound such as phenol or asubstituted phenol. Viscous poly(1-propene) or poly(1-butene) made by aprocess of this invention when used to alkylate phenol givespreferentially the para-substituted alkylation product which has somespecial advantages as viscosity improves, and the like. The alkylatedphenol product when reacted with materials such as formaldehyde andtetraethylenepentamine forms a useful lubricating oil dispersant such asthe Mannich additive.

Another very useful functionalization reaction of the terminalvinylidene bond of the polymers of this invention is the reaction of apoly(1-olefin) with maleic anhydride (an Ene reaction) which terminatesthe polymer with a succinic anhydride. Such materials are useful forpetroleum additives, paper sizing agents, adhesives, and the like.

Other useful functionalization reactions of the terminal vinylidene bondthat produce compounds of great utility are hydroformylation with carbonmonoxide and hydrogen, hydrosilylation with a silane such as aalkoxysilane or alkoxychlorosilane, epoxidation with hydrogen peroxideor a peracid, halogenation with chlorine or bromine, hydrohalogenationhydrogenation sulfonation with sulfonic acid, and the like. Theformation of these products generally proceed in the manner in whichsimple 1-olefins do may be understood by one skilled in the art.

The low molecular weight, viscous, essentially terminally-unsaturated,essentially 1-olefin polymers and copolymers of this invention may beused for lubricating oils, gasoline additives, sealants, caulks,adhesives, cosmetics, oil field chemicals, and the like. They havedistinct advantages over viscous polybutenes for one or more of theseapplications as they:

have higher reactivity due to the steric character of the terminalolefinic link;

have different viscosity/molecular weight relationships than currentviscous polyolefins;

can have higher reactivity than current viscous polyolefins after beingderivatized due to the steric character of the terminal olefin; and.

have potentially higher number average molecular weights which arelarger than current viscous polyolefins.

The functionalized products made using a phenol or substituted phenol,maleic anhydride, an epoxidizing agent, a hydrosilylating agent orcarbon monoxide and hydrogen, and the like, and of the low molecularweight, viscous, essentially-terminally unsaturated, essentially1-olefin polymers and copolymers of this invention are also useful forlubricating oils, gasoline additives, sealants, caulks, adhesives,cosmetics, and the like.

Low molecular weight, viscous, essentially-terminally unsaturated,essentially 1-olefin polymers and copolymers of this invention may bechlorinated with any of a variety of reagents including elementalchlorine and the chlorinated product then reacted with any of a varietyof amines, e.g. ethylene diamine, to obtain aminated product useful infuel and motor oil compositions. See, for example, U.S. Pat. Nos.3,960,515; 4,832,702; 4,234,235; and WO 92/14806 the disclosures ofwhich are incorporated herein by reference.

The following Examples will serve to illustrate certain specificembodiments of the herein disclosed invention. These Examples shouldnot, however, be construed as limiting the scope of the novel inventioncontained herein as there are many variations which may be made thereonwithout departing from the spirit of the disclosed invention, as thoseof skill in the art will recognize.

EXAMPLES

All manipulations with the metallocene and aluminoxane cocatalyst werecarried out in a glove box under nitrogen, and high vacuum techniqueswere used where appropriate. Determination of the degree of unsaturationof a poly(1-olefin) was measured either by epoxidation of 1-olefin withm-chloroperbenzoic acid and titration of benzoic acid produced, orreaction of 1-olefin with bromine and measurement of unreacted bromine.Determination of the amount of terminal vinylidene in a polymer samplewas carried out using ¹³ C and ¹ H NMR by integration of the peak areasin olefinic regions. Molecular weights were determined using gelpermeation chromatography(GPC).

Example 1

A butane-butene feed stock having an approximate composition of 8%propane, 9% propene, 39% isobutane, 14% 1-butene, 12% n-butane, 2%isobutylene 15% cis and trans 2-butenes, 0.5% butadiene and smallamounts (less than 1%) of other hydrocarbons) was polymerized using Ind₂ZrCl₂ and methylaluminoxane as the catalyst system. A reaction vesselwas sequentially charged with 6.7 mg of Ind₂ ZrCl₂, 25 mL of toluene and2.0 mL of a solution of MAO in toluene (d=0.860 g/mL, 5.9 wt. % Al,Al/Zr of about 220). The mixture was stirred for about 5 minutesfollowed by addition of 93 g of the above feed. The reaction mixture wasstirred at 40° C. for 20 hr, quenched with isopropanol, extracted intopentane, washed with 2N NaOH and water and dried over MgSO₄. Removal ofvolatile liquids under reduced pressure resulted in recovery of 10.8 g(61% yield based on the propene and 1-butene content) of a clear,viscous material. ¹³ C NMR showed major peaks at 109.9-110.1,112.3-112.5, 145.0-145.3 and 150.5-150.8 ppm. The presence of four peaksindicated chain termination with both propene and butene. A ¹ Hmultiplet in the range of 4.6 to 4.8 ppm was also found, and a terminalvinylidene content of greater than 80% was calculated for the product.Using similar feed stocks and the Ind₂ ZrCl₂ and methylaluminoxanecatalyst system, polymers with M_(n) in a range from about 500 to about5000 are obtained under controlled temperatures of polymerization in atemperature range of from about -10° C. to about 100° C. Using Cp₂ ZrCl₂and methylaluminoxane catalyst system, polymers with M_(n) in a rangefrom about 300 to about 2000 are obtained under controlled temperaturesof polymerization in a temperature range of from about -10° C. to about100° C.

Example 2

Example 1 is repeated using a butane-butene feed stock having anapproximate composition 4% propane, 6% propene, 31% isobutane, 14%1-butene, 12% n-butane, 17% isobutylene, 16% cis and trans 2-butenes,0.5% butadiene and small (less than 1%) of other hydrocarbons). A clear,viscous material is recovered having a terminal vinylidene content ofgreater than 80%. Using similar feed stocks and the Ind₂ ZrCl₂ andmethylaluminoxane catalyst system, polymers with M_(n) in a range fromabout 500 to about 5000 are obtained under controlled temperatures ofpolymerization in a temperature range of from about -10° C. to about100° C. Using Cp₂ ZrCl₂ and aluminoxane catalyst system, polymers withM_(n) in a range from about 300 to about 2000 are obtained undercontrolled temperatures of polymerization in a temperature range of fromabout -10° C. to about 100° C.

Example 3

Example 1 is repeated using a butane-butene feed stock having anapproximate composition 4% isobutane, 28% 1-butene, 10% n-butane, 42%isobutylene, 16% cis and trans 2-butenes, and small amounts (less than1%) of other hydrocarbons). 137 g of this feed stock was polymerized at40° C. with a Ind₂ ZrCl₂ and methylaluminoxane catalyst system. A clear,viscous material, 22 g with M_(n) of 674, was recovered. ¹³ C NMR showedthe four peaks indicated chain termination with both propene and butene.A ¹ H multiplet in the range of 4.6 to 4.8 ppm was also found, and aterminal vinylidene content of greater than 80% was calculated for theproduct. Using similar feed stocks and the Ind₂ ZrCl₂ andmethylaluminoxane catalyst system, polymers with M_(n) in a range fromabout 500 to about 5000 are obtained under controlled temperatures ofpolymerization in a temperature range of from about -10° C. to about100° C. Using Cp₂ ZrCl₂ and aluminoxane catalyst system, polymers withM_(n) in a range from about 300 to about 2000 are obtained undercontrolled temperatures of polymerization in a temperature range of fromabout -10° C. to about 100° C.

Example 4

Example 1 is repeated using a butane-butene feed stock having anapproximate composition 8% isobutane, 46% 1-butene, 17% n-butane, 27%cis and trans 2-butenes, and small amount (less than 1%) of otherhydrocarbons). A clear, viscous material is recovered having a terminalvinylidene content of greater than 80%. Using similar feed stocks andthe Ind₂ ZrCl₂ and methylaluminoxane catalyst system, polymers withM_(n) in a range from about 500 to about 5000 are obtained undercontrolled temperatures of polymerization in a temperature range of fromabout -10° C. to about 100° C. Using Cp₂ ZrCl₂ and aluminoxane catalystsystem, polymers with M_(n) in a range from about 300 to about 2000 areobtained under controlled temperatures of polymerization in atemperature range of from about -10° C. to about 100° C.

Example 5

In this example propane-propene feed stocks varying in the relativeamount of propane from 0% propane and 100% propene to 70% propane and30% propene are polymerized in a series of runs. In each run a reactionvessel is sequentially charged with 6.7 mg of Ind₂ ZrCl₂, 25 mL oftoluene and 2.0 mL of a solution of MAO in toluene (d=0.860 g/mL, 5.9wt. % Al, Al/Zr of about 220). This mixture is stirred for about 5minutes followed by addition of feed stock at a constant pressure of 40psig. The reaction mixture is stirred at 23° C. for 20 hr, quenched withisopropanol, extracted into pentane, washed with 2N NaOH and water anddried over MgSO₄. A clear, viscous material is recovered having aterminal vinylidene content of greater than 80%. Using similar feedstocks and the Ind₂ ZrCl₂ and methylaluminoxane catalyst system,polymers with M_(n) in a range from about 500 to about 5000 are obtainedunder controlled temperatures of polymerization in a temperature rangeof from about -10° C. to about 100° C. Using Cp₂ ZrCl₂ and aluminoxanecatalyst system, polymers with M_(n) in a range from about 300 to about2000 are obtained under controlled temperatures of polymerization in atemperature range of from about -10° C. to about 100° C.

Example 6

In this example pentane-pentene feed stocks varying in the relativeamount of 1-pentene from 5% 1-pentene and 95% pentane to 50% 1-penteneand 50% pentane are polymerized in a series of runs. In each run areaction vessel is sequentially charged with 6.7 mg of Ind₂ ZrCl₂, 25 mLof toluene and 2.0 mL of a solution of MAO in toluene (d=0.860 g/mL, 5.9wt. % Al, Al/Zr of about 220). This mixture is stirred for about 5minutes followed by addition of feed stock at a constant pressure. Thereaction mixture is stirred at 23° C. for 20 hr, quenched withisopropanol, extracted into pentane, washed with 2N NaOH and water anddried over MgSO₄. Removal of volatile liquid under reduced pressureresults in recovery of a clear, viscous material. ¹³ C NMR shows majorpeaks at 112.3-112.5 and 145.0-145.3 ppm, a ¹ H multiplet in the rangeof 4.6 to 4.8 ppm, and a terminal vinylidene content of greater than80%. The product has a M_(n) in a range from about 500 to about 5000 areobtained at controlled temperatures of polymerization temperature in arange from about -10° C. to about 100° C. Using similar feed stocks Cp₂ZrCl₂ and aluminoxane catalyst system, polymers with M_(n) in a rangefrom about 300 to about 2000 are obtained under controlled temperaturesof polymerization in a temperature range of from about -10° C. to about100° C.

Example 7

A 20 mL to 10 mL ratio of 1-hexene and 7-methyl-1,6-octadiene ratio waspolymerized in toluene at 50° C. using 4.5 mg of Ind₂ ZrCl₂ and analuminoxane to metallocene ratio of 330 to give a clear, free flowingviscous polymer which exhibits a M_(n) of 1170 and a DI(dispersivityindex) of 1.51 using GPC. ¹³ C NMR analysis shows two types of olefiniclinkages, terminal vinylidene and side chain. Analysis shows that aboutone molecule of diene per two hexene molecules has been incorporated inthe chain.

Preparative Example 1

A reaction vessel was sequentially charged with 6.7 mg of Ind₂ ZrCl₂, 25mL of toluene and 2.0 mL of a solution of MAO in toluene (d=0.860 g/mL,5.9 wt. % Al, Al/Zr of about 220). This mixture was stirred for about 5minutes followed by addition of propylene at a constant pressure of 40psig. The reaction mixture was stirred at 23° C. for 20 hr, quenchedwith isopropanol, extracted into pentane, washed with 2N NaOH and waterand dried over MgSO₄. Removal of volatile liquid under reduced pressureresulted in recovery of 135 g of a clear, viscous material. ¹³ C NMRshowed major peaks at 112.3-112.5 and 145.0-145.3 ppm, a ¹ H multipletin the range of 4.6 to 4.8 ppm, and a terminal vinylidene content ofgreater than 90% was calculated. This product, identified aspoly(1-propylene) PEx-1, had a M_(n) of 2325 and a M_(w) /M_(n) of 1.73.

Preparative Example 2

The polymerization of Example 1 was repeated, except the temperature ofpolymerization was 53° C. A polymer, identified as poly(1-propylene)PEx-2, with M_(n) of 987 and a M_(w) /M_(n) of 1.70 was recovered.

Preparative Example 3

A reaction vessel was sequentially charged with 8.1 mg of Cp₂ ZrCl₂, 50mL of toluene and 2.2 mL of a solution of MAO in toluene (d=0.860 g/mL,5.9 wt. % Al, Al/Zr of about 150). The mixture was stirred for about 5minutes followed by addition of propylene at 40 psig for 1 hr. Thereaction mixture was stirred at 50° C. for 1 hr, quenched withisopropanol, extracted into pentane, washed with 2N NaOH and water anddried over MgSO₄. Removal of the liquid under reduced pressure resultedin recovery of 15.0 g of a clear, viscous material. ¹³ C NMR showedmajor peaks at 112.3-112.5 and 145.0-145.3 ppm a ¹ H multiplet at4.6-4.8 ppm and the polymer exhibits a terminal vinylidene content of90%. This product, identified as poly(1-propylene) PEx-3, has a M_(n) of477 and a M_(w) /M_(n) of 2.18.

Preparative Example 4

A reaction vessel was sequentially charged with 6.7 mg of Ind₂ ZrCl₂, 25mL of toluene and 2.0 mL of a solution of MAO in toluene (d=0.868 g/mL,5.9 wt. % Al, Al/Zr of about 220). The mixture was stirred for about 5minutes followed by addition of 200 g of 1-butene. The reaction mixturewas stirred at 40° C. for 20 hours, quenched with isopropanol, extractedinto pentane, washed with 2N NaOH and water and dried over MgSO₄.Removal of the liquid under reduced pressure resulted in recovery of 190g (95% yield) of a clear, viscous material. ¹³ C NMR showed major peaksat 108-112 and 149-152 ppm and a ¹ H multiplet at 4.6-4.8 ppm. Analysisshowed the terminal vinylidene content to be greater than 80%. This,identified as poly(1-butene) PEx-4, product has a M_(n) of 1860 and aM_(w) /M_(n) of 1.64. It is possible to obtain polymers with an M_(n)ranging from about 500 to 5000 with the catalyst by varying thepolymerization temperature from -10° C. to 100° C.

Preparative Example 5

A reaction vessel was sequentially charged with 5.0 mg of Cp₂ ZrCl₂, 25mL of toluene and 2.0 mL of a solution of MAO in toluene (d=0.860 g/mL,5.9 wt. % Al, Al/Zr of about 220). The mixture was stirred for about 5minutes followed by addition of 200 g of 1-butene. The reaction mixturewas stirred at 40° C. for 20 hr, quenched with isopropanol, extractedinto pentane, washed with 2N NaOH and water and dried over MgSO₄.Removal of the liquid under reduced pressure resulted in recovery of 160g (80% yield) of a clear, viscous material. ¹³ C NMR showed major peaksat 108-112 and 149-152 ppm and a 1H multiplet in the range of 4.6 to 4.8ppm. The terminal vinylidene content of the product was greater than80%. This product, identified as poly(1-butene) PEx-5, had a M_(n) of661 and a M_(w) /M_(n) of 1.92. It is possible to obtain polymers withan M_(n) ranging from about 300 to 2000 with the catalyst by varying thepolymerization temperature from -10° C. to 100° C.

Preparative Example 6

A reaction vessel was sequentially charged with 6.7 mg of Ind₂ ZrCl₂, 25mL of toluene and 2.0 mL of a solution of MAO in toluene (d=0.860 g/mL,5.9 wt. % Al, Al/Zr of about 220). The mixture was stirred for about 5minutes followed by addition of 200 g of 1-hexene. The reaction mixturewas stirred at 40° C. for 20 hr, quenched with isopropanol, extractedinto pentane, washed with 2N NaOH and water and dried over MgSO₄.Removal of the liquid under reduced pressure resulted in recovery of 190g (95% yield) of a clear, viscous material. ¹³ C NMR showed major peaksat 108-112 and 149-152 ppm, a ¹ H multiplet in the range of 4.6-4.8 ppmand a terminal vinylidene content of greater than 80%. This product,identified as poly(1-hexene) PEx-6, had a M_(n) of 2653 and a M_(w)/M_(n) of 2.19. It is possible to obtain polymers with an M_(n) rangingfrom about 500 to 5000 with the catalyst by varying the polymerizationtemperature from -10° C. to 100° C.

Preparative Example 7

A 20 mL to 10 mL ratio of 1-hexene and 7-methyl-1,6-octadiene ratio waspolymerized in toluene at 50° C. using 4.5 mg of Ind₂ ZrCl₂ and analuminoxane to metallocene ratio of 330 to give a clear, free flowingviscous polymer which exhibits a M_(n) of 1170 and a DI (dispersivityindex) of 1.51 using GPC. ¹³ C NMR analysis shows two types of olefiniclinkages, terminal vinylidene and side chain. Analysis shows that aboutone molecule of diene per two hexene molecules has been incorporated inthe chain.

Preparative Example 8

In this example five selected metallocene catalysts systems were usedunder similar conditions. In each run a reaction vessel was sequentiallycharged with 5 mg of metallocene, 25 mL of toluene and 2.0 mL of asolution of MAO in toluene (d=0.860 g/mL, 5.9 wt. % Al, Al/Zr of about220). The mixture was stirred for about 5 minutes followed by additionof 180 g of 1-butene. The reaction mixture was stirred at 40° C. for 20hr, quenched with isopropanol, extracted into pentane, washed with 2NNaOH and water and dried over MgSO₄. Removal of the liquid under reducedpressure resulted in recovery of a clear, viscous material. ¹³ C NMRshowed major peaks at 108-112 and 149-152 ppm, a ¹ H multiplet in therange of 4.6-4.8 ppm and a terminal vinylidene content of greater than80% for each product. The metallocenes used and M_(n) of each productobtained are listed below.

    ______________________________________                                        Table of Preparative Example 8                                                         Metallocene                                                                              M.sub.n                                                   ______________________________________                                               Cp.sub.2 ZrCl.sub.2                                                                    566                                                             (MeCp).sub.2 ZrCl.sub.2   600                                                 (BuCp).sub.2 ZrCl.sub.2   565                                                 (Me.sub.5 Cp).sub.2 ZrCl.sub.2 1513                                           Ind.sub.2 ZrCl.sub.2      1755                                              ______________________________________                                    

Example 8

A 9 g portion of a poly(1-propene) made in the manner of PreparativeExample 2 (VPO MW 987) was placed in a Monel container along with 0.0145g of platinum divinyltetramethyldisiloxane catalyst and 2.02 g ofmethyldichlorosilane. The container was sealed and heated to 80° C. for3 hr. Upon cooling the product was transferred into a round-bottom flaskand the excess silane removed by vacuum stripping. The final productshowed a conversion of 83.5% as determined by comparison of the residualolefin content with the starting polymer. This conversion was alsoconfirmed by determination of the amount of silane reacted. Similarresults were obtained by employing H₂ PtCl₆ as the catalyst.

Example 9

A 9 g portion of poly(1-butene) made in the manner of PreparativeExample 5 (GPC M_(n) 760) was placed in a Monel container along with0.013 g of platinum divinyltetramethyldisiloxane catalyst and 1.8 g ofmethyldichlorosilane. The container was sealed and heated to 80° C. for3 hr. Upon cooling the product was transferred into a round-bottom flaskand the excess silane removed by vacuum stripping. The final productshowed a conversion of 81% as determined by comparison of the residualolefin content with the starting polymer. This conversion was alsoconfirmed by determination of the amount of silane reacted. Similarresults were obtained by employing H₂ PtCl₆ as the catalyst.

Comparative Example 9

This Example was run similarly to Examples 8 and 9 except that a 10 gportion of Amoco polybutene of grade H-100, 0.0145 g of platinumdivinyltetramethyldisiloxane and 2 g of methyldichlorosilane were used.The conversion was 5.3%.

Example 10

The epoxidation of a 10 g portion poly(1-butene) made in the manner ofPreparative Example 4 was carried out in 100 mL of chloroform to whichwas added 1.1 equivalents of m-chloroperbenzoic acid. The peracid wasabout 75% pure. The solution was refluxed for one hour and worked up bypouring it onto cracked ice in water and extracting the product intochloroform. The chloroform layer was subsequently extracted with a 10%sodium bicarbonate solution to remove acid. NMR analysis of the productafter removal of the chloroform by rotary evaporation showed noremaining olefin and essentially 100% conversion to the epoxide.

Example 11

To a 2 liter autoclave was charged 500 g of a poly(1-butene) made in themanner of Preparative Example 4 with a molecular weight of 1922 made inthe manner of Example 2. To this was added a 28 g portion (1.1 molarexcess) of maleic anhydride. The autoclave was sealed and heated to atemperature of approximately 220° C. and held for a specified period oftime. The autoclave was then cooled and the resulting product removedand analyzed for its conversion to the succinic anhydride derivative.Under these conditions a conversion of about 61% was obtained. Under thesame reaction conditions a conventional polybutene sample of similarmolecular weight gave a conversion of about 42%.

Example 12

A 300 mL stainless steel autoclave was charged with a 30 g portion ofpoly-(1-butene) made in the manner of Preparative Example 5 with a M_(n)of 489, 115 mL of hexene and a 1.0 g portion of dicobalt octacarbonyl.The autoclave was sealed and purged of oxygen by pressurizing thereactor to 90 psig with a 2/1 H₂ /CO gas mixture, stirring for fewmoments and then slowly venting the pressure. This procedure wasrepeated twice. The pressure was adjusted to 2500 psig and the solutionheated to 180° C. After reaching reaction temperature, the pressure wasreadjusted to 3000 psig and the solution allowed to stir for 3 hr underthese conditions. After this time, the solution was cooled to roomtemperature and slowly vented to atmospheric pressure. The crude darkred-brown solution was washed with refluxing 10% acetic acid until theorganic layer was colorless. The layers were separated and the organiclayer washed with water and dried over MgSO₄. Analysis was performedusing silica gel chromatography employing first pentane and thenchloroform/acetone as solvents. Conversion of poly(1-butene) topoly(1-butylalcohol) and poly(1-butylformate) was 87%.

Example 13

The procedure employed in Example 12 was followed using poly-(1-butene)made in the manner of Preparative Example 4 with a M_(n) 1098.Conversion to poly-butylalcohol and poly-1-butylformate (as determinedby silica gel chromatography) was 84%.

Example 14

A portion of a poly-(1-propene) made in the manner of PreparativeExample 2 (M_(n) about 900) was chlorinated at 0.1 SCFH chlorine attemperatures above 100° C. The resulting polypropyl chloride contained8.2% chloride. This chlorinated viscous polymer was reacted with anexcess of aliphatic diamine for several hours at reflux. The resultingaminated polypropene had a basic nitrogen content of 1.75 wt % which issuitable for a variety of uses including detergents and other fueladditives.

What is claimed is:
 1. A viscous terminally unsaturated copoly(1-olefin)formed from two or more C₃ -C₂₀ linear 1-olefins and having a molecularweight of about 300 to about 10,000 and a terminal vinylidene content ofmore than 80%.
 2. The viscous terminally unsaturated copoly(1-olefin) ofclaim 1 having a terminal vinylidene content of at least about 90% and amolecular weight of about 300 to about
 5000. 3. The viscous terminallyunsaturated copoly(1-olefin) of claim 1 having a terminal vinylidenecontent of at least about 95% and a molecular weight of about 400 toabout
 3000. 4. The viscous terminally unsaturated copoly(1-olefin) ofclaim 1 formed from a mixture of propylene and 1-butene.
 5. The viscousterminally unsaturated copoly(1-olefin) of claim 1 formed from propyleneand at least one C₄ -C₂₀ linear 1-olefin.
 6. The viscous terminallyunsaturated copoly(1-olefin) of claim 1 formed from 1-butene and atleast one C₅ -C₂₀ linear 1-olefin.
 7. The viscous terminally unsaturatedcopoly(1-olefin) of claim 1 formed from propylene and a C₄ -C₁₀ linear1-olefin.
 8. The viscous terminally unsaturated copoly(1-olefin) ofclaim 1 formed from propylene and a C₄ -C₆ linear 1-olefin.
 9. Theviscous terminally unsaturated copoly(1-olefin) of claim 1 formed from1-butene and a C₅ -C₁₀ linear 1-olefin.
 10. The viscous terminallyunsaturated copoly(1-olefin) of claim 1 formed from 1-butene and a C₅-C₆ linear 1-olefin.
 11. The viscous terminally unsaturatedcopoly(1-olefin) of claim 1 having a terminal vinylidene content of morethan 90%.
 12. The viscous terminally unsaturated copoly(1-olefin) ofclaim 1 having a terminal vinylidene content of more than 95%.
 13. Theviscous terminally unsaturated copoly(1-olefin) of claim 1 having aterminal (1-olefin) content of more than 98%.
 14. The viscous terminallyunsaturated copoly(1-olefin) of claim 1 having a terminal (1-olefin)content of more than 99%.
 15. The viscous terminally unsaturatedcopoly(1-olefin) of claim 1 having a molecular weight of about 300 toabout
 5000. 16. The viscous terminally unsaturated copoly(1-olefin) ofclaim 1 having a molecular weight of about 400 to about
 3000. 17. Theviscous terminally unsaturated copoly(1-olefin) of claim 1 having amolecular weight of about 1000 to about
 2000. 18. The viscous terminallyunsaturated copoly(1-olefin) of claim 15 formed from a mixture ofpropylene and 1-butene.
 19. The viscous terminally unsaturatedcopoly(1-olefin) of claim 15 formed from propylene and at least one C₄-C₂₀ linear 1-olefin.
 20. The viscous terminally unsaturatedcopoly(1-olefin) of claim 15 formed from propylene and at least oneC4-C₁₀ linear 1-olefin.
 21. The viscous terminally unsaturatedcopoly(1-olefin) of claim 15 formed from propylene and at least one C₄-C₂₀ linear 1-olefin and having a terminal vinylidene content of morethan 90%.
 22. The viscous terminally unsaturated copoly(1-olefin) ofclaim 15 formed from propylene and at least one C₄ -C₂₀ linear 1-olefinand having a terminal vinylidene content of more than 95%.
 23. Theviscous terminally unsaturated copoly(1-olefin) of claim 15 formed frompropylene and at least one C₄ -C₂₀ linear 1-olefin and having a terminal(1-olefin) content of more than 98%.
 24. The viscous terminallyunsaturated copoly(1-olefin) of claim 15 formed from propylene and atleast one C₄ -C₂₀ linear 1-olefin and having a terminal (1-olefin)content of more than 99%.
 25. The viscous terminally unsaturatedcopoly(1-olefin) of claim 15 formed from 1-butene and at least one C₅-C₂₀ linear 1-olefin.
 26. The viscous terminally unsaturatedpoly(1-olefin) of claim 15 formed from 1-butene and at least one C₅ -C₁₀linear 1-olefin.
 27. The viscous terminally unsaturated poly(1-olefin)of claim 15 formed from 1-butene and at least one C₅ -C₂₀ linear1-olefin and having a terminal vinylidene content of more than 90%. 28.The viscous terminally unsaturated copoly(1-olefin) of claim 15 formedfrom 1-butene and at least one C₅ -C₂₀ linear 1-olefin and having aterminal vinylidene content of more than 95%.
 29. The viscous terminallyunsaturated copoly(1-olefin) of claim 15 formed from 1-butene and atleast one C₅ -C₂₀ linear 1-olefin and having a terminal (1-olefin)content of more than 98%.
 30. The viscous terminally unsaturatedcopoly(1-olefin) of claim 15 formed from 1-butene and at least one C₅-C₂₀ linear 1-olefin and having a terminal (1-olefin) content of morethan 99%.